JP2735816B2 - Oxazolinone derivatives, method for producing the same and herbicides - Google Patents
Oxazolinone derivatives, method for producing the same and herbicidesInfo
- Publication number
- JP2735816B2 JP2735816B2 JP7208607A JP20860795A JP2735816B2 JP 2735816 B2 JP2735816 B2 JP 2735816B2 JP 7208607 A JP7208607 A JP 7208607A JP 20860795 A JP20860795 A JP 20860795A JP 2735816 B2 JP2735816 B2 JP 2735816B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- group
- oxazolinone
- following general
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- UPULOMQHYQDNNT-UHFFFAOYSA-N 5h-1,3-oxazol-2-one Chemical class O=C1OCC=N1 UPULOMQHYQDNNT-UHFFFAOYSA-N 0.000 title claims description 14
- 239000004009 herbicide Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- 230000002363 herbicidal effect Effects 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 claims description 6
- 235000008206 alpha-amino acids Nutrition 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 2
- KCOPAESEGCGTKM-UHFFFAOYSA-N 1,3-oxazol-4-one Chemical compound O=C1COC=N1 KCOPAESEGCGTKM-UHFFFAOYSA-N 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 230000035784 germination Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 240000007594 Oryza sativa Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000021307 Triticum Nutrition 0.000 description 5
- 241000209140 Triticum Species 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 244000062793 Sorghum vulgare Species 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241001148659 Panicum dichotomiflorum Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 244000061457 Solanum nigrum Species 0.000 description 3
- 235000002594 Solanum nigrum Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- FDPPHZFAQZDEJU-UHFFFAOYSA-N ethyl 2-[(3-chlorobenzoyl)amino]-2-(4-methylphenyl)propanoate Chemical compound C=1C=C(C)C=CC=1C(C)(C(=O)OCC)NC(=O)C1=CC=CC(Cl)=C1 FDPPHZFAQZDEJU-UHFFFAOYSA-N 0.000 description 3
- 238000009331 sowing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 240000006995 Abutilon theophrasti Species 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000207892 Convolvulus Species 0.000 description 2
- 244000299507 Gossypium hirsutum Species 0.000 description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 2
- 235000007244 Zea mays Nutrition 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- -1 m-chlorobenzamido Chemical group 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PREJKGYAASSDHK-UHFFFAOYSA-N 2-[(3-chlorobenzoyl)amino]-2-(4-methylphenyl)propanoic acid Chemical compound C1=CC(C)=CC=C1C(C)(C(O)=O)NC(=O)C1=CC=CC(Cl)=C1 PREJKGYAASSDHK-UHFFFAOYSA-N 0.000 description 1
- WHIHIKVIWVIIER-UHFFFAOYSA-N 3-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC(Cl)=C1 WHIHIKVIWVIIER-UHFFFAOYSA-N 0.000 description 1
- 244000144706 Aeschynomene indica Species 0.000 description 1
- 235000004051 Aeschynomene indica Nutrition 0.000 description 1
- 241000544785 Bromus japonicus Species 0.000 description 1
- JGLVJGQAOWWMAA-UHFFFAOYSA-N C1=CC(C)=CC=C1C1(NC(=O)C=2C=C(Cl)C=CC=2)N=CC(=O)O1 Chemical compound C1=CC(C)=CC=C1C1(NC(=O)C=2C=C(Cl)C=CC=2)N=CC(=O)O1 JGLVJGQAOWWMAA-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000017896 Digitaria Nutrition 0.000 description 1
- 241001303487 Digitaria <clam> Species 0.000 description 1
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 1
- 240000003176 Digitaria ciliaris Species 0.000 description 1
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 1
- 235000005476 Digitaria cruciata Nutrition 0.000 description 1
- 235000006830 Digitaria didactyla Nutrition 0.000 description 1
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 1
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 235000014716 Eleusine indica Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 235000009432 Gossypium hirsutum Nutrition 0.000 description 1
- STECJAGHUSJQJN-USLFZFAMSA-N LSM-4015 Chemical compound C1([C@@H](CO)C(=O)OC2C[C@@H]3N([C@H](C2)[C@@H]2[C@H]3O2)C)=CC=CC=C1 STECJAGHUSJQJN-USLFZFAMSA-N 0.000 description 1
- 235000003990 Monochoria hastata Nutrition 0.000 description 1
- 240000000178 Monochoria vaginalis Species 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000011999 Panicum crusgalli Nutrition 0.000 description 1
- 241000287127 Passeridae Species 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 244000184734 Pyrus japonica Species 0.000 description 1
- 235000007230 Sorghum bicolor Nutrition 0.000 description 1
- 244000067505 Xanthium strumarium Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 241001148683 Zostera marina Species 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000013096 assay test Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000021374 legumes Nutrition 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/36—One oxygen atom
- C07D263/42—One oxygen atom attached in position 5
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、除草剤として優れ
た効果を有する新規なオキサゾリノン系誘導体及びその
製造方法に関する。[0001] The present invention relates to a novel oxazolinone derivative having an excellent effect as a herbicide and a method for producing the same.
【０００２】[0002]
【従来の技術】従来オキサゾリン誘導体のあるものは、
殺虫剤として知られている。しかしながら、オキサゾリ
ノン構造を有する除草剤は、いまだ知られていない。2. Description of the Related Art Some oxazoline derivatives have been
Known as insecticides. However, a herbicide having an oxazolinone structure has not yet been known.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、優れた除草
効果を有する、新規なオキサゾリノン系誘導体を提供す
ることを目的とする。An object of the present invention is to provide a novel oxazolinone derivative having an excellent herbicidal effect.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、このため
鋭意検討を重ねた結果、下記の一般式（Ｉ）で示される
オキサゾリノン系誘導体が、優れた除草効果を有するこ
とを見出し、本発明を完成した。すなわち、本発明は、
下記一般式（Ｉ）で示されるオキサゾリノン系誘導体で
ある。Means for Solving the Problems The inventors of the present invention have conducted intensive studies, and as a result, have found that oxazolinone derivatives represented by the following general formula (I) have an excellent herbicidal effect. Completed the invention. That is, the present invention
An oxazolinone derivative represented by the following general formula (I).
【０００５】[0005]
【化３】 Embedded image
【０００６】（式中、Ｒは低級アルキル基、又はハロゲ
ン、低級アルキル及び／若しくはトリフルオロメチルが
置換したフェニル基を表し、Ａは窒素原子又は炭素原子
を表し、Ｘはハロゲン原子、メトキシカルボニル基、ニ
トロ基、又はハロゲン若しくはトリフルオロメチルが置
換したフェノキシ基を表し、ｎは１〜３の整数を表し、
ｎが２又は３のとき、Ｘは互に同一でも異なっていても
よい）(Wherein, R represents a lower alkyl group or a phenyl group substituted by halogen, lower alkyl and / or trifluoromethyl, A represents a nitrogen atom or a carbon atom, X represents a halogen atom, a methoxycarbonyl group. Represents a nitro group, or a phenoxy group substituted by halogen or trifluoromethyl, n represents an integer of 1 to 3,
when n is 2 or 3, Xs may be the same or different from each other)
【０００７】上記オキサゾリノン系誘導体（Ｉ）は、下
記一般式（II）で示されるα−アミノ酸を、下記一般式
（III)で示される酸クロリドと縮合反応させ、得られた
下記一般式（IV）で示されるアミノ基が置換されたα−
アミノ酸を無水酢酸と脱水反応させて製造することがで
きる。The oxazolinone derivative (I) is obtained by subjecting an α-amino acid represented by the following general formula (II) to a condensation reaction with an acid chloride represented by the following general formula (III) to obtain the following general formula (IV) Α-substituted amino group represented by
It can be produced by dehydrating an amino acid with acetic anhydride.
【０００８】[0008]
【化４】 Embedded image
【０００９】（式中、Ｒ、Ｘ、Ａ及びｎはそれぞれ前記
と同じ。Ｒ′は低級アルキル基を示す）(Wherein, R, X, A and n are the same as above, and R 'represents a lower alkyl group)
【００１０】本発明の新規なオキサゾリノン系誘導体の
製造方法において、重要な原料（II）は、α位に二つ置
換されたα−アミノ酸である。該化合物（II）の合成方
法としては、種々列挙されるが、収率よく簡単に製造す
る方法としては、下記のとおりケトンからヒダントイン
を経て、加水分解させる方法を用いる（Goodson et a
l., J. Org. Chem. 1960, 25, 1920参照）。In the process for producing a novel oxazolinone derivative of the present invention, an important raw material (II) is an α-amino acid having two substitutions at the α-position. Various methods for synthesizing the compound (II) are listed, and as a method for easily producing the compound in good yield, a method for hydrolyzing a ketone via a hydantoin as described below is used (Goodson et a.
l., J. Org. Chem. 1960, 25, 1920).
【００１１】[0011]
【化５】 Embedded image
【００１２】（式中、Ｒ及びＲ′は前記と同じ）(Wherein R and R 'are the same as above)
【００１３】したがって、本発明の新規なオキサゾリノ
ン系誘導体（Ｉ）の製造方法は、出発物質として一般式
（II）のα−アミノ酸を、置換基を有する一般式（III)
の酸クロリドと縮合反応させ、一般式（IV）のアミノ基
が置換された中間体のα−アミノ酸を得る。このものを
無水酢酸と反応させ、脱水反応を経てオキサゾリノン系
誘導体（Ｉ）を製造する。Accordingly, the process for producing the novel oxazolinone derivative (I) according to the present invention comprises, as a starting material, an α-amino acid of the general formula (II) and a compound of the general formula (III) having a substituent.
To give an intermediate α-amino acid substituted with an amino group of the general formula (IV). This is reacted with acetic anhydride to produce an oxazolinone derivative (I) through a dehydration reaction.
【００１４】以上により製造されるオキサゾリノン系誘
導体（Ｉ）を有効成分とする除草剤は、粒剤、水和剤、
乳剤に製剤し、農作物の発芽前及び発芽後に使用され
る。発芽前に用いる場合は、農作物の種を播種する以
前、播種中又は播種後、農作物が発芽する以前に土壌を
処理する。また、発芽後に用いる場合は、植物が発芽し
た後、又は植物の生育期間中に適用する。すなわち、本
発明に係る除草剤は、土壌処理の試験結果、禾本科雑草
よりも広葉雑草に対する防除効果がよく、特に、発芽後
適用すると Black nightshade ；Solanum nigrum L. 、
イチビ；Abutilon avicennaeに対する効果が優れ、禾本
科植物のトウモロコシ；Zea Mays L. 、小麦；Triticum
aestinum 、及び稲；Oryza sativa L. に対し相対的に
安定性を維持し得る。また、淡水処理試験でヒエ；Echi
nochloabicolor Moench 、コナギ；Monochoria vaginal
isに対する防除効果がよく、稲に対する薬害は微弱であ
るので、除草剤として優れている。The herbicides containing the oxazolinone derivative (I) produced as described above as an active ingredient include granules, wettable powders,
It is formulated into an emulsion and used before and after germination of crops. When used before germination, the soil is treated before, during or after sowing the crop seed and before the crop germinates. When used after germination, it is applied after the germination of the plant or during the growing period of the plant. That is, the herbicide according to the present invention has a better control effect on broadleaf weeds than grass weeds as a result of soil treatment test, and particularly when applied after germination, Black nightshade; Solanum nigrum L. ,
It has excellent effect on Abutilon avicennae , and maize of cereal plants; Zea Mays L. , wheat; Triticum
aestinum and rice; can maintain relative stability to Oryza sativa L. Further, barnyard freshwater treatment test; Echi
nochloabicolor Moench , Konagi ; Monochoria vaginal
It is an excellent herbicide because it has a good control effect on is and little phytotoxicity on rice.
【００１５】[0015]
【実施例】以下、本発明を実施例によって具体的に説明
するが、本発明はこれらの実施例により限定されるもの
ではない。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
【００１６】実施例１：２−（ｍ−クロロベンズアミ
ド）−２−（ｐ−トリル）プロピオン酸エチルの合成 ２−アミノ−２−（ｐ−トリル）プロピオン酸エチル
４．２ｇ（０．０２M ）とトリエチルアミン３ｇ（０．
０３M ）とをジクロロメタン４０mlに溶かし、ｍ−クロ
ロベンゾイルクロリド３．５ｇ（０．０２M ）をジクロ
ロメタン５mlに溶かした溶液を前記溶液に徐々に滴下し
た。その後、常温で１時間攪拌した後、反応液を水で洗
滌して乾燥した後、溶媒を除去し、２−（ｍ−クロロベ
ンズアミド）−２−（ｐ−トリル）プロピオン酸エチル
６．５ｇ（収率：９５％）を得た。Example 1: Synthesis of ethyl 2- (m-chlorobenzamido) -2- (p-tolyl) propionate 4.2 g (0.02M) of ethyl 2-amino-2- (p-tolyl) propionate And 3 g of triethylamine (0.
03M) was dissolved in 40 ml of dichloromethane, and a solution of 3.5 g (0.02M) of m-chlorobenzoyl chloride in 5 ml of dichloromethane was gradually added dropwise to the solution. After stirring at room temperature for 1 hour, the reaction solution was washed with water and dried, the solvent was removed, and 6.5 g of ethyl 2- (m-chlorobenzamido) -2- (p-tolyl) propionate ( (Yield: 95%).
【００１７】実施例２：２−（ｍ−クロロベンズアミ
ド）−２−（ｐ−トリル）プロピオン酸の合成 水酸化カリウム１．２ｇ（０．０２M ）をエタノール３
０mlと水５mlとの混合溶液に溶かした液に、実施例１で
得た２−（ｍ−クロロベンズアミド）−２−（ｐ−トリ
ル）プロピオン酸エチル３．５ｇ（０．０１M ）を添加
した。この反応溶液を１時間加熱した後、冷却し、エタ
ノールを減圧留去し、pH２になるまで２N ＨＣｌ溶液を
加えた後、ジクロロメタンにて抽出した。同抽出液を乾
燥して減圧留去し、標題の化合物２．９ｇ（収率：９２
％）を得た。Example 2: Synthesis of 2- (m-chlorobenzamido) -2- (p-tolyl) propionic acid 1.2 g (0.02 M) of potassium hydroxide was added to ethanol 3
To a solution dissolved in a mixed solution of 0 ml and 5 ml of water was added 3.5 g (0.01 M) of ethyl 2- (m-chlorobenzamido) -2- (p-tolyl) propionate obtained in Example 1. . After heating the reaction solution for 1 hour, it was cooled, ethanol was distilled off under reduced pressure, a 2N HCl solution was added until the pH reached 2, and the mixture was extracted with dichloromethane. The extract was dried and evaporated under reduced pressure to give 2.9 g of the title compound (yield: 92
%).
【００１８】実施例３：２−（ｍ−クロロベンズアミ
ド）−２−（ｐ−トリル）オキサゾリン−５−オンの合
成 実施例２で得た２−（ｍ−クロロベンズアミド）−２−
（ｐ−トリル）プロピオン酸エチル３．１７ｇ（０．０
１M ）を無水酢酸３０mlに溶かした後、１時間加熱還流
した。反応液を冷却した後、過量の無水酢酸を減圧留去
し、残渣をクロマトグラフィーにより純粋な油相の目的
化合物２．４ｇ（収率：８０％）を得た。 NMR(CDCL3) 1.83(s, 3H), 2.32(s, 3H), 7.13-8.13(m,
8H).Example 3 Synthesis of 2- (m-chlorobenzamido) -2- (p-tolyl) oxazolin-5-one 2- (m-chlorobenzamido) -2- obtained in Example 2
3.17 g of ethyl (p-tolyl) propionate (0.0
1M) was dissolved in 30 ml of acetic anhydride and heated under reflux for 1 hour. After cooling the reaction solution, excess acetic anhydride was distilled off under reduced pressure, and the residue was subjected to chromatography to obtain 2.4 g (yield: 80%) of the target compound as a pure oil phase. NMR (CDCL 3 ) 1.83 (s, 3H), 2.32 (s, 3H), 7.13-8.13 (m,
8H).
【００１９】出発物質と酸クロリドとを変えて、実施例
１、２及び３と同様に実施して、表１、２及び３に示し
た化合物を得た。また同表にそれぞれの化合物のＮＭＲ
（ＣＤＣｌ3)データ及び収率を併記した。By following the same procedures as in Examples 1, 2 and 3 except that the starting material and the acid chloride were changed, the compounds shown in Tables 1, 2 and 3 were obtained. The table also shows the NMR of each compound.
(CDCl 3 ) data and yield are also shown.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【表３】 [Table 3]
【００２３】実施例４：除草活性検定試験 滅菌された砂質養土に適量の肥料を混合し、試験用ポッ
ト（３４８cm2 ）に入れた。播種口を設けた後、実験用
雑草又は作物種子（モロコシ；Sorghum bicolor Moenc
h、ケイヌビエ；Echinochloa crus-galli P. Beauv 、
スズメノチャヒキ；Bromus japonicus Thumb ex Murr、
メヒシバ；Digitaria sangunalis (L) Scop 、Fall pan
icum；Panicum dichotomiflorum Michex、ヒルガオ；Ca
lystegia japonica Choisy、オナモミ；Xanthium strum
arium L.、イチビ；Abutilon avicennae Gaertn 、クサ
ネム；Aeschynomene indica L.、Black nightshade；So
lanum nigrum L. 、トウモロコシ；Zea mays L. 、マ
メ；Glycine max (L) Merr、ワタ；Gossypium hirsutum
L. 、コムギ；Triticum aestirum L.、イネ；Oryza sa
tiva L. ）を播種し、篩にかけた土で覆土し、温室に置
く。Example 4 Herbicidal Activity Assay Test An appropriate amount of fertilizer is mixed with the sterilized sandy soil, and
To (348cmTwo ). After setting up the seeding port, for experiment
Weeds or crop seeds (sorghum;Sorghum bicolor Moenc
h, Cainubie;Echinochloa crus-galli P. Beauv ,
Sparrow Butterfly;Bromus japonicus Thumb ex Murr,
Crabgrass;Digitaria sangunalis (L) Scop , Fall pan
icum;Panicum dichotomiflorum Michex, Convolvulus;Ca
lystegia japonica Choisy, Onami fir;Xanthium strum
arium L., Strawberries;Abutilon avicennae Gaertn , Kusa
Nem;Aeschynomene indica L., Black nightshade;So
lanum nigrum L. ,corn;Zea mays L. , Ma
Me;Glycine max (L) Merr,Water;Gossypium hirsutum
L. , Wheat;Triticum aestirum L., Rice;Oryza sa
tiva L. ), Covered with sieved soil and placed in a greenhouse
Good.
【００２４】次いで、試験用化合物（表１の１４及び１
５化合物）を表４に示した量、アセトン溶媒に溶かした
後、非イオン性界面活性剤（Tween-20）を添加した水で
それぞれ１：１になるように希釈し、ポット当たり１４
mlを撒布した。発芽前土壌処理は播種後１日目に、発芽
後の茎葉処理は播種後８〜１２日目に製剤された薬剤で
処理した。薬剤処理した後温室内で２〜３週間育て、こ
れらの除草効果を生理学的に観察・調査した。すなわ
ち、無防除の場合を０、完全防除の場合を１００とし、
１１等級に分割してそれらの除草活性を評価し、７０以
上の等級を実質的に植物に対し除草効果を有するもので
あると判断した。その結果を表４に示した。Next, the test compounds (14 and 1 in Table 1)
5 compounds) were dissolved in an acetone solvent in the amounts shown in Table 4 and then diluted 1: 1 with water to which a nonionic surfactant (Tween-20) was added.
ml was sprayed. The soil treatment before germination was performed on the first day after sowing, and the foliage treatment after germination was performed on the 8th to 12th days after sowing with the prepared chemical. After the chemical treatment, the plants were grown in a greenhouse for 2 to 3 weeks, and their herbicidal effects were physiologically observed and investigated. That is, 0 for no control, 100 for complete control,
The herbicidal activities were evaluated by dividing them into 11 grades, and a grade of 70 or more was judged to have a substantial herbicidal effect on plants. Table 4 shows the results.
【００２５】[0025]
【表４】 [Table 4]
【００２６】表４に示したように、低い濃度においても
除草効果が優れ、発芽前処理よりも発芽後の処理が優秀
な効果を奏するということがわかる。更に、単子葉植物
（トウモロコシ、マメ、ワタ、コムギ、イネ、モロコ
シ、ヒエ）より、双子葉植物（Fall panicum、Black ni
ghtshade、クサネム、イチビ、ヒルガオ）に対して一層
良い効果を奏することがわかる。As shown in Table 4, it can be seen that the herbicidal effect is excellent even at a low concentration, and that the post-emergence treatment is more effective than the pre-emergence treatment. Furthermore, dicotyledonous plants (Fall panicum, Black ni) from monocotyledonous plants (maize, legume, cotton, wheat, rice, sorghum, and millet)
ghtshade, kusanem, ichibi, convolvulus).
【００２７】[0027]
【発明の効果】本願発明の新規なオキサゾリノン系誘導
体は、実施例に示したように特に双子葉植物に対して優
れた効果のある除草剤である。As described in Examples, the novel oxazolinone derivatives of the present invention are herbicides having excellent effects particularly on dicotyledonous plants.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｄ 213:63 263:42） (56)参考文献 西独国特許出願公開2139641（ＤＥ, Ａ) ＩＮＴ．Ｊ．ＰＥＰＴＩＤＥ ＰＲＯ ＴＥＩＮ ＲＥＳ．ＶＯＬ．38 （1991），Ｐ．242−252 ＢＩＯＣＨＥＭＩＳＴＲＹ ＶＯＬ. ８，ＮＯ．５（1969），Ｐ．1967−1974Continuation of the front page (51) Int.Cl. 6 Identification symbol FI C07D 213: 63 263: 42) (56) References West German Patent Application Publication 2139641 (DE, A) INT. J. PEPTIDE PRO TEIN RES. VOL. 38 (1991), p. 242-252 BIOCHEMISTRY VOL. 8, NO. 5 (1969), p. 1967-1974
Claims (3)
ノン系誘導体。 【化１】 （式中、Ｒは低級アルキル基、又はハロゲン、低級アル
キル及び／若しくはトリフルオロメチルが置換したフェ
ニル基を表し、Ａは窒素原子又は炭素原子を表し、Ｘは
ハロゲン原子、メトキシカルボニル基、ニトロ基、又は
ハロゲン若しくはトリフルオロメチルが置換したフェノ
キシ基を表し、ｎは１〜３の整数を表し、ｎが２又は３
のとき、Ｘは互に同一でも異なっていてもよい。ただ
し、Ａが炭素原子であり、Ｘがハロゲン原子又はニトロ
基のとき、Ｒは低級アルキル基ではない。）1. An oxazolinone-based derivative represented by the following general formula (I). Embedded image (Wherein, R represents a lower alkyl group or a phenyl group substituted by halogen, lower alkyl and / or trifluoromethyl, A represents a nitrogen atom or a carbon atom, X represents a halogen atom, a methoxycarbonyl group, or a nitro group. Or a phenoxy group substituted by halogen or trifluoromethyl, n represents an integer of 1 to 3, and n represents 2 or 3
In this case, Xs may be the same or different from each other. However, when A is a carbon atom and X is a halogen atom or a nitro group, R is not a lower alkyl group. )
酸を、下記一般式（III)で示される酸クロリドと縮合反
応させ、得られた下記一般式（IV）で示されるアミノ基
が置換されたα−アミノ酸を無水酢酸と脱水反応させる
請求項１のオキサゾリノン系誘導体の製造方法。 【化２】 （式中、Ｒ、Ｘ、Ａ及びｎはそれぞれ前記と同じ。Ｒ′
は低級アルキル基を表す）2. An α-amino acid represented by the following general formula (II) is subjected to a condensation reaction with an acid chloride represented by the following general formula (III) to obtain an amino group represented by the following general formula (IV). The method for producing an oxazolinone derivative according to claim 1, wherein the substituted α-amino acid is dehydrated with acetic anhydride. Embedded image (Wherein, R, X, A and n are the same as above. R ′
Represents a lower alkyl group)
リノン系誘導体を有効成分とする除草剤。3. A herbicide comprising an oxazolinone derivative represented by the formula (I) as an active ingredient.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940020300A KR0125130B1 (en) | 1994-08-17 | 1994-08-17 | Oxazolinones derivatives and process for the preparing thereof and use |
| KR20300/1994 | 1994-08-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0859637A JPH0859637A (en) | 1996-03-05 |
| JP2735816B2 true JP2735816B2 (en) | 1998-04-02 |
Family
ID=19390560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7208607A Expired - Fee Related JP2735816B2 (en) | 1994-08-17 | 1995-08-16 | Oxazolinone derivatives, method for producing the same and herbicides |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5691278A (en) |
| JP (1) | JP2735816B2 (en) |
| KR (1) | KR0125130B1 (en) |
| DE (1) | DE19530123C2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6130337A (en) * | 1997-04-11 | 2000-10-10 | Board Of Trustees Of Leland Stanford Junior University | Enantiomerically enriched α,α-distributed amino acids and method |
| US6551777B1 (en) | 1999-02-25 | 2003-04-22 | Exact Sciences Corporation | Methods for preserving DNA integrity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2139641A1 (en) | 1971-08-07 | 1973-02-15 | Bayer Ag | 2-(4-chlorobenzamido)-alkanamides - with hypnotic and tranquillizing activity |
-
1994
- 1994-08-17 KR KR1019940020300A patent/KR0125130B1/en not_active IP Right Cessation
-
1995
- 1995-08-16 DE DE19530123A patent/DE19530123C2/en not_active Expired - Fee Related
- 1995-08-16 US US08/515,608 patent/US5691278A/en not_active Expired - Fee Related
- 1995-08-16 JP JP7208607A patent/JP2735816B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2139641A1 (en) | 1971-08-07 | 1973-02-15 | Bayer Ag | 2-(4-chlorobenzamido)-alkanamides - with hypnotic and tranquillizing activity |
Non-Patent Citations (2)
| Title |
|---|
| ＢＩＯＣＨＥＭＩＳＴＲＹ ＶＯＬ．８，ＮＯ．５（１９６９），Ｐ．１９６７−１９７４ |
| ＩＮＴ．Ｊ．ＰＥＰＴＩＤＥ ＰＲＯＴＥＩＮ ＲＥＳ．ＶＯＬ．３８（１９９１），Ｐ．２４２−２５２ |
Also Published As
| Publication number | Publication date |
|---|---|
| KR0125130B1 (en) | 1997-12-05 |
| JPH0859637A (en) | 1996-03-05 |
| US5691278A (en) | 1997-11-25 |
| DE19530123C2 (en) | 1997-02-20 |
| KR960007584A (en) | 1996-03-22 |
| DE19530123A1 (en) | 1996-02-22 |
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